Journal
CRYSTALS
Volume 10, Issue 3, Pages -Publisher
MDPI
DOI: 10.3390/cryst10030235
Keywords
X-ray; fluorescence; UV-Vis; CuO NPs; Cu2+ ions; Schiff base
Funding
- Ministerio de Ciencia, Innovacion y Universidades of Spain [RTI2018-099222-B-I00]
- Union Europea (Fondo europeo de desarrollo regional) [RTI2018-099222-B-I00]
- Direccion Xeral de I+D-Xunta de Galicia
- Grupos de Referencia Competitiva [ED431C2018/19]
- Strategic Grouping in Materials AEMAT [ED431 E2018/0]
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The present study deals with the investigation of Cu2+, Ni2+ and Pd2+ chelating potential of the Schiff base, (E)-N-(2-((2-hydroxybenzylidene)amino)benzyl)-4-methylbenzenesulfonamide (H2SB). Crystal structures of Ni(HSB)(2), Pd(HSB)(2) and Cu(HSB)(2) have been elucidated from single crystal X-ray diffraction data. NMR spectroscopy showed the presence of two conformers of Pd(HSB)(2) in solution, both with an E configuration of the ligand. The determination of binding constants by fluorescence quenching showed that affinity of H2SB to Cu2+ in solution is higher than for Ni2+ and Pd2+. Since there is a high demand for selective, sensitive, rapid and simple methods to detect copper in aqueous samples (both as Cu2+ ions and as CuO NPs), we have explored H2SB as an optical chemosensor. H2SB interacts with increasing concentrations of Cu2+ ions, giving rise to a linear increase in the absorbance of a band centered at about 392 nm. H2SB displays a high selectivity toward Cu2+, even in the presence of the most common metal ions in water (Ca2+, Mg2+, Na+, K+, Al3+ and Fe3+), and some heavy transition metal ions such as the soft acids Pd2+ and Cd2+. H2SB also interacts with increasing concentrations of CuO NPs, which gives rise to a linear decrease in its fluorescence intensity (lambda(em) = 500 nm, lambda(ex) = 390 nm). Quenching has occurred as a result of the formation of a non-fluorescent ground-state surface complex H2SB-CuO NPs. The limits of detection and quantification of CuO NPs were 9.8 mg/L and 32.6 mg/L, respectively. The presence of TiO2, Ag and Au NPs does not interfere with the determination of CuO NPs.
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